CN113416360A - Electron irradiation crosslinked polyethylene material and preparation method thereof - Google Patents
Electron irradiation crosslinked polyethylene material and preparation method thereof Download PDFInfo
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- CN113416360A CN113416360A CN202110505224.8A CN202110505224A CN113416360A CN 113416360 A CN113416360 A CN 113416360A CN 202110505224 A CN202110505224 A CN 202110505224A CN 113416360 A CN113416360 A CN 113416360A
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000004719 irradiation crosslinked polyethylene Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 25
- 239000006229 carbon black Substances 0.000 claims abstract description 54
- -1 vinyl guanamine Chemical compound 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 32
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 29
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 29
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 25
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 15
- 229920004889 linear high-density polyethylene Polymers 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims description 46
- 239000004698 Polyethylene Substances 0.000 claims description 29
- 229920000573 polyethylene Polymers 0.000 claims description 29
- 238000001125 extrusion Methods 0.000 claims description 27
- 239000008187 granular material Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 17
- 229920001721 polyimide Polymers 0.000 claims description 16
- 239000009719 polyimide resin Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000011265 semifinished product Substances 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000009461 vacuum packaging Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 150000008065 acid anhydrides Chemical class 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 7
- 238000009472 formulation Methods 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006112 polar polymer Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Abstract
The invention discloses an electron irradiation crosslinked polyethylene material which comprises the following components in parts by weight: 30-50 parts of linear low-density polyethylene; 5-8 parts of high-density polyethylene; 5-8 parts of a polyurethane elastomer; 1-5 parts of low dielectric resin containing anhydride; 1-5 parts of vinyl guanamine; 0.1 to 1 portion of carbon black; 0.1 to 1 portion of cross-linking agent. The invention takes linear low-density polyethylene and high-density polyethylene as main materials, takes a polyurethane elastomer, low-dielectric resin containing anhydride and vinyl guanamine as auxiliary materials, and leads the main carbon chains and branch carbon chains to form a more complex three-dimensional network structure under the action of electronic irradiation and a cross-linking agent, so as to improve the mechanical strength and the heat resistance of the cable, meet the requirement of higher high temperature resistance of the cable after the current 3G signal is increased to 5G signal, and evenly disperse carbon black in the three-dimensional network structure, so as to improve the crack resistance, the high temperature aging resistance and the antistatic property of the system.
Description
Technical Field
The invention relates to the technical field of polyethylene, in particular to an electron irradiation crosslinking polyethylene material and a preparation method thereof.
Background
Polyethylene is a thermoplastic resin prepared by polymerizing ethylene, and has the advantages of no odor, no toxicity, good low-temperature resistance, good chemical stability, good corrosion resistance, excellent electrical insulation property and the like, so that the polyethylene becomes one of the cable materials with the largest using amount, most of the existing cable sheath materials are polyethylene materials, along with the application of cables in more fields, the application environment of the cables is more and more complicated, the requirements on various performances of the cables are more and more high, in addition, the frequency of the cables is improved due to the fact that 3G signals are increased to 5G signals, the heat productivity is greatly increased, the requirement on the temperature resistance grade of the cables is higher, and the performance of the cables prepared by using a single polyethylene material cannot meet the requirements on the application environment of the cables.
The cable cross-linking mode mainly comprises two modes: chemical crosslinking and physical crosslinking. Chemical crosslinking is further classified into dry crosslinking and warm water crosslinking. Dry crosslinking is the crosslinking of polyethylene molecular chains over a certain period of time in a high-pressure gas at temperatures of up to 300 ℃ and 400 ℃. The warm water crosslinking is to immerse the cable in warm water at 90 ℃ for 5-7 hours to crosslink the polyethylene molecular chains. Physical crosslinking is also called irradiation crosslinking, namely high-energy electron beam emitted by an electron accelerator is utilized to bombard a cable insulation or sheath layer to break a macromolecular chain, the broken first point is called a free radical, and the free radicals are unstable and need to be recombined with each other, and the original chain molecular structure is changed into a three-dimensional network molecular structure after being recombined to form crosslinking.
Patent CN107880350A discloses a high temperature resistant polyethylene modified cable material, which comprises filler, composite heat stabilizer, low polymerization degree polyethylene, high polymerization degree polyethylene, coupling agent and cross-linking agent, wherein the polymerization degree of polyethylene resin is controlled by adding the filler to improve the high temperature resistant performance, and the highest melting point is 103 ℃. Patent CN111154224A discloses a high temperature resistant cable insulation layer material, which comprises phenolic resin, polyethylene, polystyrene, zinc oxide, ethylene propylene diene monomer, polyethylene wax and plasticizer, wherein the high temperature resistant performance of the cable insulation layer material is improved by the action of the ethylene propylene diene monomer and the plasticizer. The high-temperature-resistant cables in the patent are all cables prepared by a chemical crosslinking method, have low temperature-resistant grade and cannot meet the requirement of higher high-temperature-resistant performance of the existing cables.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide an electron irradiation crosslinked polyethylene material which has a higher temperature resistance level and meets the requirement of higher high temperature resistance of the cable after the current 3G signal is increased to the 5G signal.
The second purpose of the present invention is to provide a preparation method of electron irradiation crosslinked polyethylene material, which is simple and easy to control, and can be applied to large-scale production.
One of the purposes of the invention is realized by adopting the following technical scheme:
an electron irradiation cross-linked polyethylene material comprises the following components in parts by weight:
30-50 parts of linear low-density polyethylene; 5-8 parts of high-density polyethylene; 5-8 parts of a polyurethane elastomer; 1-5 parts of low dielectric resin containing anhydride; 1-5 parts of vinyl guanamine; 0.1 to 1 portion of carbon black; 0.1 to 1 portion of cross-linking agent.
Further, the linear low density polyethylene has a melt index of 0.8-1.2g/10min and a density of 0.918-0.925g/m3(ii) a The high-density polyethylene has a melt index of 0.7-1.5g/10min and a density of 0.947-0.953g/m3. According to the invention, by selecting the matching of the linear low-density polyethylene and the high-density polyethylene, the linear low-density polyethylene has no long branched chain and only short branched chain, and has higher penetration resistance and tensile strength; the high-density polyethylene has high insulating dielectric strength, molecules are in a linear structure, and the branching phenomenon is less, so that a high-molecular chain is broken in the process of electron irradiation of the material, and a carbon branched chain of a main chain carbon chain formed by recombination is shorter, so that the influence of the branched chain on the addition of other branched chains is avoided. The higher the melt index, the lower the relative molecular mass, the better the flowability. The linear low density polyethylene and the high density polyethylene with low and not large difference in melt index are selected to generate similar reaction speed of free radicals in the process of electron irradiation, so that the three-dimensional crosslinking net structure obtained after recombination is more compact.
Further, the polyurethane elastomer has a melt index of 9.0-13.0g/10min and a Shore A hardness of 93-95. The polyurethane elastomer is a high polymer material which can be melted by heating and has the characteristics of high strength, high elasticity, wear resistance, oil resistance, low temperature resistance and the like, and is a repeating structural unit which is formed by forming a soft section by a flexible long chain of oligomer polyol (poly epsilon-caprolactone diol), forming a hard section by diisocyanate and a chain extender (1, 4-butanediol) and alternately arranging the hard section and the soft section through a one-step method. Preferably, the poly-epsilon-caprolactone diol: diisocyanate: the mass ratio of the 1, 4-butanediol is 1: (2-3): (1-2). The invention adopts the polyurethane elastomer which is 10 times larger than the melt index of the polyethylene, in the process of electron irradiation, partial high molecular chains of the polyurethane elastomer are cut off again and grafted to the branched chains of the polyethylene again to improve the wear resistance and the heat resistance of the polyethylene, and the residual polyurethane elastomer reduces the irradiation amount required by irradiation crosslinking under the action of a crosslinking agent, generates new free radicals, improves the degree of microphase separation of the polyurethane elastomer and increases the dispersibility of carbon black in the polyurethane elastomer.
Further, the low dielectric resin containing acid anhydride is maleic anhydride graft modified polyimide resin, and the dielectric constant of the resin is less than 3 at the frequency of 10 GHz. The electron irradiation crosslinked polyethylene material is commonly used as an insulating layer of a cable, the dielectric constant of the insulating layer is an important factor of impedance matching, the impedance matching can allow high-speed high-frequency signals, and in order to realize high speed of the high-frequency signals, the dielectric constant of the insulating layer needs to be reduced. The maleic anhydride graft modified polyimide resin is introduced into the polyethylene material by a radiation crosslinking method to reduce the dielectric constant of the surface thereof. The polyimide resin has the characteristics of heat resistance, low temperature resistance, excellent mechanical property, good processing property, no toxicity and the like, but has poor compatibility with polar polymers, and after the maleic anhydride is grafted and modified, the compatibility of the polyimide resin with the polar polymers can be increased, so that the polyimide resin can be better dispersed, and is convenient for further reaction in the later electronic irradiation process. Preferably, the grafting ratio of the maleic anhydride graft-modified polyimide resin is 20 to 40%.
Furthermore, the crosslinking agent is TAC (2, 4, 6-triallyloxy-1, 3, 5-triazine), and is a crosslinking agent for three-functionality reaction, so that the strength, rigidity and heat resistance of the product can be obviously improved. The radiation crosslinking, cracking and irradiation dose of the high molecular material are closely related, the increase of the irradiation dose can promote the cracking of the material while promoting the crosslinking degree, in order to avoid the low irradiation dose to have low influence on the generation of free radicals of the polyurethane elastomer and the low dielectric resin containing the anhydride, the crosslinking agent TAC is added, and when the irradiation dose is low, the crosslinking agent TAC is firstly generated to promote other substances to generate free radicals to carry out polymerization reaction, so that the cracking of the polyethylene material is reduced, and the crosslinking degree is improved.
Further, the carbon black comprises a first carbon black having a low specific surface area and a second carbon black having a high specific surface area, the first carbon black having a specific surface area of 140m2/g-180m2(ii)/g; the second carbon black has a specific surface area of 350m2/g-420m2(ii) in terms of/g. The cable can become brittle when exposed to the sun, and is easy to carry static electricity, the addition of the carbon black is beneficial to improving the crack resistance, high-temperature aging resistance and antistatic performance of a system, but simultaneously brings the problems of easy agglomeration and uneven dispersion. Preferably, the mass ratio of the first carbon black to the second carbon black is 1: (0.5-1). The first carbon black and the second carbon black are hydrophobic carbon black subjected to surface treatment by dimethyldichlorosilane.
Further, the mass ratio of the polyurethane elastomer, the anhydride-containing low dielectric resin, the vinyl guanamine and the crosslinking agent is 1: (0.5-0.8): 0.5: (0.05-0.1). The vinyl guanamine is rich in polymerizability, and can be introduced into a high molecular branch chain under the excitation of a high-energy electron beam of electron irradiation, so that the softening point temperature and the glass body transfer point temperature of a product are greatly improved, and the relative density is also increased. In the proportion of compounding with the cross-linking agent, the polymer chains of all materials can be well broken again under low irradiation, and then recombined, so that the materials can be connected to the branched chains of polyethylene, and the performance of the polyethylene is greatly improved. Preferably, the mass ratio of the polyurethane elastomer, the anhydride-containing low dielectric resin, the vinylguanamine and the crosslinking agent is 1: 0.6: 0.5: 0.08.
the second purpose of the invention is realized by adopting the following technical scheme:
a preparation method of an electron irradiation crosslinking polyethylene material comprises the following preparation steps:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation to obtain granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder to complete crosslinking under the irradiation of electrons, so as to form the electron irradiation crosslinked polyethylene material.
Further, in step S3, the extrusion temperature of the semi-finished product extruder is 110-125 ℃; in step S4, the extrusion temperature of the finished product extruder is 125-135 ℃; the irradiation dose of electron irradiation is 105kGy-120 kGy.
Compared with the prior art, the invention has the beneficial effects that:
the electronic irradiation crosslinking polyethylene material provided by the invention takes linear low-density polyethylene and high-density polyethylene as main materials, takes a polyurethane elastomer, low-dielectric resin containing anhydride and vinyl guanamine as auxiliary materials, and breaks the high molecular chains of the main materials and the auxiliary materials under the action of electronic irradiation and a crosslinking agent, the high molecular chains of the main materials form main carbon chains, the high molecular chains of the auxiliary materials form branch carbon chains, and active bonds in the auxiliary materials form free radicals, so that the main carbon chains and the branch carbon chains form a more complex three-dimensional network structure, the mechanical strength and the heat resistance of the cable are improved, the requirement of higher high-temperature resistance of the cable after the current 3G signal is increased to 5G signal is met, and carbon black is uniformly dispersed in the three-dimensional network structure, so that the anti-cracking performance, the high-temperature aging resistance and the antistatic performance of a system are improved.
The preparation method is simple and easy to control, and can be applied to large-scale production.
The preparation method of the invention changes the extrusion temperature of the semi-finished product and the finished product, the extrusion temperature of the semi-finished product is suitable for melting of the linear low density polyethylene, other materials can be dispersed in the semi-finished product to form a wrapping state, the extrusion temperature of the finished product is further increased, the activity of the other materials and the cross-linking agent is favorably improved, the cross-linking reaction is carried out under lower auxiliary amount, and the heat resistance of the structure obtained by the reaction is better.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment. The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified. In the following examples, the linear low density polyethylene has a melt index of 1.2g/10min and a density of 0.918g/m, unless otherwise specified3(ii) a The high density polyethylene has a melt index of.5 g/10min and a density of 0.953g/m3. The polyurethane elastomer has a melt index of 13.0g/10min and a Shore A hardness of 94.
Example 1:
an electron irradiation cross-linked polyethylene material comprises the following components in parts by weight:
30 parts of linear low-density polyethylene; 5 parts of high-density polyethylene; 5 parts of polyurethane elastomer; 1 part of low dielectric resin containing acid anhydride; 1 part of vinyl guanamine; 0.1 part of carbon black; 0.1 part of cross-linking agent TAC. Wherein the low dielectric resin containing acid anhydride is maleic anhydride graft modified polyimide resin with the grafting rate of 20 percent; the carbon black comprises the following components in percentage by mass of 1: 150m of 0.52First carbon Black in g and 350m2A second carbon black per gram.
The preparation method of the electron irradiation crosslinking polyethylene material comprises the following preparation steps:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation, wherein the extrusion temperature is 120 ℃, obtaining granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder, the extrusion temperature is 125 ℃, and crosslinking is completed under the electron irradiation with the irradiation dose of 105kGy, so as to form the electron irradiation crosslinked polyethylene material.
Example 2:
an electron irradiation cross-linked polyethylene material comprises the following components in parts by weight:
40 parts of linear low-density polyethylene; 6 parts of high-density polyethylene; 6 parts of a polyurethane elastomer; 3 parts of low dielectric resin containing anhydride; 3 parts of vinyl guanamine; 0.5 part of carbon black; 0.5 part of cross-linking agent TAC. Wherein the low dielectric resin containing acid anhydride is maleic anhydride graft modified polyimide resin with the grafting rate of 20 percent; the carbon black comprises the following components in percentage by mass of 1: 150m of 0.52First carbon Black in g and 350m2A second carbon black per gram.
The preparation method of the electron irradiation crosslinking polyethylene material comprises the following preparation steps:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation, wherein the extrusion temperature is 120 ℃, obtaining granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder, the extrusion temperature is 125 ℃, and crosslinking is completed under the electron irradiation with the irradiation dose of 105kGy, so as to form the electron irradiation crosslinked polyethylene material.
Example 3:
an electron irradiation cross-linked polyethylene material comprises the following components in parts by weight:
50 parts of linear low-density polyethylene; 8 parts of high-density polyethylene; 8 parts of polyurethane elastomer; 5 parts of low dielectric resin containing anhydride; 5 parts of vinyl guanamine; 1 part of carbon black; and 1 part of a crosslinking agent TAC. Wherein the low dielectric resin containing acid anhydride is maleic anhydride graft modified polyimide resin with the grafting rate of 20 percent; the carbon black comprises the following components in percentage by mass of 1: 150m of 0.52First carbon Black in g and 350m2A second carbon black per gram.
The preparation method of the electron irradiation crosslinking polyethylene material comprises the following preparation steps:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation, wherein the extrusion temperature is 120 ℃, obtaining granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder, the extrusion temperature is 125 ℃, and crosslinking is completed under the electron irradiation with the irradiation dose of 105kGy, so as to form the electron irradiation crosslinked polyethylene material.
Example 4:
an electron irradiation cross-linked polyethylene material comprises the following components in parts by weight:
50 parts of linear low-density polyethylene; 5 parts of high-density polyethylene; 5 parts of polyurethane elastomer; 3 parts of low dielectric resin containing anhydride; 2.5 parts of vinyl guanamine; 0.5 part of carbon black; 0.4 part of cross-linking agent TAC. Wherein the low dielectric resin containing acid anhydride has a graft ratio20% of maleic anhydride graft modified polyimide resin; the carbon black comprises the following components in percentage by mass of 1: 150m of 0.52First carbon Black in g and 350m2A second carbon black per gram.
The preparation method of the electron irradiation crosslinking polyethylene material comprises the following preparation steps:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation, wherein the extrusion temperature is 120 ℃, obtaining granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder, the extrusion temperature is 125 ℃, and crosslinking is completed under the electron irradiation with the irradiation dose of 105kGy, so as to form the electron irradiation crosslinked polyethylene material.
Example 5:
unlike example 4, the acid anhydride-containing low dielectric resin of example 5 is a maleic anhydride graft-modified polyimide resin having a graft ratio of 30%, specifically as follows:
an electron irradiation cross-linked polyethylene material comprises the following components in parts by weight:
50 parts of linear low-density polyethylene; 5 parts of high-density polyethylene; 5 parts of polyurethane elastomer; 3 parts of low dielectric resin containing anhydride; 2.5 parts of vinyl guanamine; 0.5 part of carbon black; 0.4 part of cross-linking agent TAC. Wherein the low dielectric resin containing acid anhydride is maleic anhydride graft modified polyimide resin with the grafting rate of 30 percent; the carbon black comprises the following components in percentage by mass of 1: 150m of 0.52First carbon Black in g and 350m2A second carbon black per gram.
The preparation method of the electron irradiation crosslinking polyethylene material comprises the following preparation steps:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation, wherein the extrusion temperature is 120 ℃, obtaining granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder, the extrusion temperature is 125 ℃, and crosslinking is completed under the electron irradiation with the irradiation dose of 105kGy, so as to form the electron irradiation crosslinked polyethylene material.
Example 6:
unlike example 4, the acid anhydride-containing low dielectric resin of example 6 is a maleic anhydride graft-modified polyimide resin having a graft ratio of 40%, specifically as follows:
an electron irradiation cross-linked polyethylene material comprises the following components in parts by weight:
50 parts of linear low-density polyethylene; 5 parts of high-density polyethylene; 5 parts of polyurethane elastomer; 3 parts of low dielectric resin containing anhydride; 2.5 parts of vinyl guanamine; 0.5 part of carbon black; 0.4 part of cross-linking agent TAC. Wherein the low dielectric resin containing acid anhydride is maleic anhydride graft modified polyimide resin with the grafting rate of 40 percent; the carbon black comprises the following components in percentage by mass of 1: 150m of 0.52First carbon Black in g and 350m2A second carbon black per gram.
The preparation method of the electron irradiation crosslinking polyethylene material comprises the following preparation steps:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation, wherein the extrusion temperature is 120 ℃, obtaining granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder, the extrusion temperature is 125 ℃, and crosslinking is completed under the electron irradiation with the irradiation dose of 105kGy, so as to form the electron irradiation crosslinked polyethylene material.
In the above embodiments, each material is not limited to the above components, and each material may also be composed of other single components or multiple components described in the present invention, and the component parts of each material are not limited to the above parts, and the component parts of each material may also be a combination of other component parts described in the present invention, and are not described herein again.
Comparative example 1
In comparison with example 1, comparative example 1 does not add the acid anhydride-containing low dielectric resin, and the rest of the formulation and the preparation method are the same as example 1.
Comparative example 2
In comparison with example 1, comparative example 2 does not add vinylguanamine, and the rest of the formulation and the preparation method are the same as example 1.
Comparative example 3
In comparison with example 1, comparative example 3 has no crosslinking agent added, and the remaining formulation and preparation method are the same as those of example 1.
Comparative example 4
In comparison with example 1, in comparative example 4, low density polyethylene was used instead of linear low density polyethylene, and the rest of the formulation and the preparation method were the same as example 1.
Comparative example 5
The irradiation dose of electron irradiation in comparative example 5 was 150kGy as compared with example 1, and the rest of the formulation and the preparation method were the same as in example 1.
Performance testing
The crosslinked polyethylene materials obtained in examples 1 to 6 and comparative examples 1 to 5 were subjected to the following performance tests, namely tensile strength GB/T0403-2006, elongation at break GB/T0403-2006, volume resistivity GB/T3048-2007 at 20 ℃, thermal elongation test GB/T2951-2008, impact embrittlement temperature GB/T5470-2008, and thermal aging test GB/T2951-2008, and the results are shown below.
TABLE 1
As can be seen from the above table, comparative example 1 has a reduced volume resistivity and a reduced insulating property due to the absence of the acid anhydride-containing low dielectric resin; comparative example 2 has a large influence on the impact embrittlement temperature, the elongation at break change rate and the like because vinylguanamine is not added; comparative example 3 because no crosslinking agent is added, the crosslinking degree is low and the influence on the performance is large at the temperature for irradiation crosslinking; comparative example 4 because the low density polyethylene replaces the linear low density polyethylene, the performance of the low density polyethylene is inferior to that of the linear low density polyethylene, and the low density polyethylene has long and short chains, lower crystallinity, lower softening point and inferior high temperature resistance, and the structure obtained by using the low density polyethylene for irradiation crosslinking has inferior performance in a high temperature resistance test; comparative example 5 has a problem that the material thereof is partially cracked due to the increase of the irradiation dose of the electron irradiation, and the performance thereof is deteriorated.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. An electron irradiation crosslinking polyethylene material is characterized by comprising the following components in parts by weight:
30-50 parts of linear low-density polyethylene; 5-8 parts of high-density polyethylene; 5-8 parts of a polyurethane elastomer; 1-5 parts of low dielectric resin containing anhydride; 1-5 parts of vinyl guanamine; 0.1 to 1 portion of carbon black; 0.1 to 1 portion of cross-linking agent.
2. The electron irradiation crosslinked polyethylene material of claim 1, wherein the linear low density polyethylene has a melt index of 0.8-1.2g/10min and a density of 0.918-0.925g/m3(ii) a The high-density polyethylene has a melt index of 0.7-1.5g/10min and a density of 0.947-0.953g/m3。
3. The electron irradiation crosslinked polyethylene material of claim 1, wherein the polyurethane elastomer has a melt index of 9.0-13.0g/10min and a shore a hardness of 93-95.
4. The electron irradiation crosslinked polyethylene material of claim 1, wherein the anhydride-containing low dielectric resin is a maleic anhydride graft-modified polyimide resin.
5. The electron irradiation crosslinked polyethylene material according to claim 4, wherein the grafting ratio of the maleic anhydride graft modified polyimide resin is 20% to 40%.
6. The electron irradiation crosslinked polyethylene material of claim 1, wherein the crosslinking agent is TAC.
7. The electron irradiation crosslinked polyethylene material according to claim 1, wherein the carbon black comprises a first carbon black having a low specific surface area and a second carbon black having a high specific surface area, the first carbon black having a specific surface area of 140m2/g-180m2(ii)/g; the second carbon black has a specific surface area of 350m2/g-420m2/g。
8. The electron irradiation crosslinked polyethylene material of claim 1, wherein the mass ratio of the polyurethane elastomer, the anhydride-containing low dielectric resin, the vinylguanamine, and the crosslinking agent is 1: (0.5-0.8): 0.5: (0.05-0.1).
9. A method for preparing an electron irradiation crosslinked polyethylene material according to any of claims 1 to 8, comprising the steps of:
s1: firstly, uniformly stirring linear low-density polyethylene, high-density polyethylene and low-dielectric resin containing anhydride at normal temperature to obtain premix;
s2: sequentially adding the polyurethane elastomer, the vinyl guanamine, the cross-linking agent and the carbon black into the premix, and uniformly stirring to obtain a cross-linking raw material;
s3: putting the cross-linked raw materials into a semi-finished product extruder for extrusion granulation to obtain granules, and storing the granules in a vacuum packaging bag;
s4: when in use, the granules are put into a finished product extruder to complete crosslinking under the irradiation of electrons, so as to form the electron irradiation crosslinked polyethylene material.
10. The method for preparing an electron irradiation crosslinked polyethylene material according to claim 9, wherein in step S3, the extrusion temperature of the semi-finished product extruder is 110 ℃ to 125 ℃; in step S4, the extrusion temperature of the finished product extruder is 125-135 ℃; the irradiation dose of electron irradiation is 105kGy-120 kGy.
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| CN113584978A (en) * | 2021-09-28 | 2021-11-02 | 山东大学 | Retaining wall type roadbed modified PE (polyethylene) tensile grating and preparation process thereof |
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| CN113584978A (en) * | 2021-09-28 | 2021-11-02 | 山东大学 | Retaining wall type roadbed modified PE (polyethylene) tensile grating and preparation process thereof |
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